Heterocyclic nitrogen-and sulfur-containing optical brightener compounds

ABSTRACT

OPTICAL BRIGHTENER COMPOUNDS AS 2-BENZISOTHIAZOLONYL-S-DIOXIDE COMPOUNDS, O-DISULFOPHENYLIMIDINYL COMPOUNDS AND BENZISOTHIAZOLYL-S-DIOXIDE COMPOUNDS THE OPTICAL ACTIVITY OF THESE COMPOUNDS CAN BE EMPLOYED TO ADVANTAGE IN THE OPTICAL BRIGHTENING OF A WIDE VARIETY OF NATURAL AND SYNTHETIC MATERIALS. THEY ARE USEFUL IN THE BRINGHTENING OF FABRICS AND FIND APPLICATION IN THE PREPARATION OF LAUNDRY DETERGENT COMPOSITIONS AND HYPOCHLORITE BLEACH-CONTAINING COMPOSITIONS.

United States PatentOflice US. Cl. 260-301 2 Claims ABSTRACT OF THE DISCLOSURE Optical brightener compounds defined as 2-benzisothiazolonyl S -'dioxide compounds, o-disulfophenylimidinyl compounds and benzisothiazolyl-S-dioxide compounds. The optical activity of these compounds can be employed to advantage in the optical brightening of a wide variety of natural and synthetic materials. They are useful in the brightening of fabrics and find application in the preparation of laundry detergent compositions and hypochlorite bleach-containing compositions.

BACKGROUND 'OF THE INVENTION This is a division of application Ser. No. 846,601, filed July 31, 1969, now issued as US. Pat. No. 3,711,474, patented Jan. 16, 1973.

This invention relates to optical brightening agents. More particularly, it relates to optical brightening agents useful in the optical brightening of a wide variety of materials and to detergent and hypochlorite bleach-containing compositions containing them.

In recent years, the use of optical brightening agents, oftentimes termed optical bleaches or fluorescers, has grown enormously. These compositions which are colorless dyestufis function by absorbing light in the ultraviolet range (300-400 nm.) such as is contained in natural daylight and remitting this as visible, blue-white light (400-500 nm.). This fluorescence masks natural yellowing of textile fibers and results in a highly desirable blue-white glow on white goods and a fresher, cleaner appearance of colored goods. The fluorescence of optical brightening agents, while in the blue range, varies somewhat in dominant wavelength. Where the dominant wavelength is longer, the blue fluorescence is considered to have a slightly greenish tinge. A shorter dominant wavelength near the violet end of the spectrum results in blue fluorescence which is slightly reddish. For practical purposes, particularly for use in laundry detergent formulations, a neutral blue fluorescence is generally preferable.

Optical brighteners suitable for textile applications must exhibit a high degree of fluorescence. Frequently, the fluorescence of conventional optical brighteners is destroyed or quenched by contact with hypochlorite and similar oxidizing bleaches. Since many of the deeply embedded soils and stains encountered in the laundering of textile fabrics are conventionally removed by the action of chemical bleaching, great eflort has been expended in the search for optical brighteners which resist the destructive elfects of hypochlorite bleaches.

Accordingly, it is an object of this invention to provide novel optical brighteners having a high degree of fluorescence and resistance to the destructive efiects of hypochlorite bleaches.

Another object of this invention is to provide detergent compositions containing an organic detergent, an alkaline builder salt and an optical brightener.

Patented Aug. 6, 1974 A further object of this invention is to provide laundry detergent compositions containing an organic detergent, analkaline builder salt, a bleaching compound and an optical brightener. I

Still another object of this invention is to provide aqueous. hypochlorite and granular bleach compositions containing an optical brightener.

Other objects of this invention will become apparent from consideration of the detailed description of the invention which appears hereinafter.

SUMMARY OF THE INVENTION The above and other objects of this invention are achieved by the present invention which comprises the provision of optical brightener compounds of the formula:

wherein each a is an integer from 1 to 4; x is 0 or 1; each A is selected from hydrogen; alkyl of 1 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, octyl, decyl), preferably of 1 to 4 carbon atoms; halogen (e.g., chlorine, bromine); alkoxy of 1 to 10 carbon atoms (e.g., methoxy, butoxy, hexyloxy, decyloxy); aryl of from 6 to 12 carbon atoms (e.g., phenyl, biphenyl, naphthyl); alkylsulfonyl of from 1 to 10 carbon atoms (e.g., methylsulfonyl, octylsulfonyl, decylsulfonyl); alkoxyalkyl of from 2 to 10 carbon atoms (e.g., methoxymethyl, butoxymethyl, ethylhexyloxymethyl); polyethylenoxy of the formula H(CH CH O),, where n is an integer from 1 to 10 (e.g., CH CH CH O) haloalkyl of from 1 to 10 carbon atoms (e.g., trifiuoromethyl, perfluoroethyl, chloroethyl); alkanoyl of from 2 to 10 carbon atoms (e.g., acetyl, propionyl, hexanoyl, octanoyl, decanoyl); cyano; polyhydroxyalkyl of from 1 to 10 carbon atoms (e.g., 1,2,3-trihydroxypropyl, sorbitol) X is selected from o o I -S; CH;; and -il-; when x is zero, Z is a monovalent radical selected from Eb Bb wherein each b is an integer from 1 to 4 and each B is defined as A above; SO OM where M is hydrogen or alkali metal; or

where R and R' are each hydrogen, alkyl of 1 to 4 carbon atoms, hydroxyalkyl of from 1 to 4 carbon atoms, aryl, glucosyl or together comprise a ring structure; and

Ap .Ap

wherein each A is as hereinbefore defined and each p is 1 or 2; and when x is one, Y and W are each selected from arid is the residue of undergo reaction with a reactive aromatic halide accordwherein each'B' and each I: are w li es mn wi Par i s a vention" vare,excellent optical brightenersfor use in a variety or natural and synthetic 'materials and are especially characterized by their resistance to the destructive action of chlorine-containing bleaching compounds. .Acl5 cordingly, they can be employed in detergent com-posi- Compounds having a 2-benzisothiazolonyl-S-dioiride', 0

tions containing alkaline builder compounds and active disulfophenylimidinyl' or"benzisothiazolyl-S-dioxide group chlorine-containing bleaching compounds and in aqueous and an additional cyclic moietyof different configuration and granular bleach compositions. correspond to the formula DETAILED DESCRIPTION OF THE INVENTION z The optical brightener derivatives of the present inveni tion having the hereinbefore defined formula are charf j acterized herein as 2-benzisothiazolonyl-S-dioxide com- T N A pounds, o-disulfophenylimidinyl compounds and benziso- V thiazolyl-S-dioxide compounds when they are character- X W a ized by the presence of wherein X, Z, Y and W are hereinbefore defined and Y and W are such as to comprise a cyclic structure difierent from that containing "group X. The compounds can be 0 0 0 0 0 0 conveniently prepared by reactingone mole ofian aroe 6 a matic diamine with one mole of reactive aromatic halide 7 1\ 7 1\ 7 1\ to form an intermediate which'is thereafter'reacted with A 2N1 I one mole of a different aromatic halide to produce the desired compound. 7 8 g; 8 g. 8 3 5 This reaction can be illustrated 'by the following reac- 9 g 9 9 tion scheme:

Hm -oH=oH-Nm groups, respectively, wherein A and n are as defined here- 40 -CH;C1 Q 1 a inbefore. 'SOzONa SOzONa The optical brighteners of the present invention are derived from fluorescent aromatic primary monoor dis Y amines characterized by ultraviolet absorption in the 310 i to 400 nanometer range and fluorescence in the 400 to 475 N- -CH=CHNH1 range. These fluorescent amines can be represented by the formula (H N) Z, wherein Z represents the residue of C SOzONa soioNa the fluorescent amine, i.e., the entire molecule exclusive of the amino group and q is one in the case of a mono- 40:01 amine and two in the case of a diamine. The equimolar 01 condensation reaction of a monoamine with a reactive aromatic dihalide to form a Z-benzisothiazolonyl-S-dioxv ide, o-disulfophenylimidinyl or benzisothiazolyl-S-dioxide s 1 1 S compound is illustrated by the following reaction scheme: 1 i

Cl SOzONa S OzONa \S/ -,The,intermediatecompound can also be prepared by other convenient methods. For example, a phthalimidinyl compound v can be prepared by equimolarz reaction of disodium 4,4-

diamino-Z,2' stilbenedisulfonate with" phthalide. Reaction of the resulting compound, disodium 4-phthalimidinyl-4'- -.amino zfl stilbenedisnlfonate, with an equimolar amount "of-i'a-chlororn toluenesulfonyl chloride-, results in the for- HQN-"Z -"NH mation of an optical brightener having-excellent fluoresa fluorescent aromatic amine as hereinbefore defined. 1 I Similarly, fluorescent aromatic diamines having the same spectral characteristics and represented as SO ONS. SO ONS. C a

disodium 4- l-phthalimidinyl) -4'- (2-benzisothiazoly1-S- dioxide)-2,2"stilbenedisulfonate The, radical Z, where employed herein is used to represent the radical derived by abstraction of one or two primary amino groups from a fluorescent aromatic amine described hereinbefore. It will be understood that this radical is considered as being derived by abstraction for convenience only and that the characterization of the amine residue in such terms is not intended to imply that abstraction in a chemical sense is actually involved in the formation of the brightener compounds of the present invention.

The amines which can be employed to prepare the optical brighteners of the present invention are fluorescent aromatic primary monoand diamines characterized by ultraviolet absorption in the range of 310 to 400 nm. and fluorescence in the 400-475 nm. range. These compounds are conventional brightener chromophores known to those skilled in the art. Examples of fluorescent amines having the prescribed spectral characteristics and their monovalent or bivalent radicals (Z) include the following:

(1) 4-aminostilbenes of the formula:

where each b is as defined above and each B is defined as A above or where M is hydrogen or an alkali metal (e.g., sodium, potassium, lithium); and R and R are each hydrogen or alkyl of 1 to 4 carbon atoms, (e.g., methyl, ethyl, n-propyl, isopropyl, sec-butyl); aryl (e.g., phenyl); glucosyl; hydroxyalkyl of l to 4 carbon atoms (e.g., Z-hydroxyethyl) or R and R' together comprise a ring structure (e.g., pyridyl, morpholino) (2) 4,4'-diaminostilbenes of the formula:

HzNQ-OIP OHQ-NE? Bb Eb Eb Bb where each b is as defined above and each B is defined the same as A above or where M is hydrogen or an alkali metal; and R and R are each hydrogen; al'kyl of 1 to 4 carbon atoms; aryl;

glycosyl; hydroxyalkyl of 1 to 4 carbon atoms or together comprise part of a ring structure; and

(3) 7-aminocoumarins of the formula:

OzOH

SOzOH the disodium salt thereof; 4-amino-4'-methoxy-2,2-stilbenedisulfonamide,

S 0 zNH: S O gNHz 4-amino-2-stilbenesulfonic acid,

SOzOH and the sodium salt thereof) and the 4,4'-diaminostilbenes (e.g., 4,4-diann'no-2,2-stilbenedisulfonic acid,

the disodium salt thereof; and 4,4-diamino-2,2'-stilbenedisulfonamide Optical brighteners derived from amines of the present invention have the following structures:

N CH=CH X/ Eb Bb wherein a, b, p, A, B and X have the meanings defined above.

Optical brighteners prepared from preferred amines have the structures:

a-szspso X $020M 8020M and wherein X, Y, W, M, R and R are as hereinbefore defined.

The mono- (X is and di- (Y is X and W are wherein x is zero, a range of about 0.3:1 to 1.5 :1 is employed. Since the reaction is nearly quantitative, a molar proportion of 1:1 of o-chlorosulfoaroyl chloride to fluorescent primary amine is preferred. In the case of the preparation of compounds having a bis-structure, i.e., those wherein x in the above described formula is one, the molar proportion of o-chlo'rosulfoaroyl chloride to fluorescent primary amine employed is from 1.8:1 to 3: 1, the ratio of 2:1 being preferred. When asymmetrical benzisothiazolonyl-S-dioxide derivatives are desired, two or more dissimilar o-chlorosulfoaroyl chlorides can be employed. Preferably, the o-chlorosulfoaroyl chlorides are sequentially reacted with the fluorescent amine.

While the reaction can be effected by reacting at a temperature of from C. to 150 C., a preferred temperature range is about 50 C. to about 100 C. Reactions conducted at the lower temperature of the suitable range, i.e., at about 0 C. normally are effected in a period of time of about 24 hours. Conversely, reactions at about 100 C. require less time and may be effected in good yield in about 30 minutes.

:The Z-benzisothiazolonykS-dioitiiie compounds-lief the invention are prepared in a polar organ-ic solvent which is essentially non-reactive to either the o-chlorosulfoaroyl chloride or fluorescent amine employed in the reaction. The amount of solvent employed is an amount-at least sufiicient to dissolve the fluorescent amine, an amount of about threetimes the weightof amine employed being sufficient. Examples of suitable essentially non-reactive solvents which can be employedarewater, alcohol s,N-,N- dialkyl low molecular weight amides such as dimethylformamide, cyclic ethers suchas tetrahydrofuran and dioXane, aromatic hydrocarbon's'such as b 'e'hzene and certain organic solvent-waterwmixtures suchl:as"-'dimethylformamicle-water, -e.g. dimethylformaimide' -montaining from about 1 to about-%? water ona'volumefvolurne The mono- (X is the formula 1 /SO: I /S(% N,-z N f I S 1 SO: X

wherein x is zero or one, will vary as in the case of reaction of an o-chlorosulfoaroyl chloride and a fluorescent primary amine described hereinbefore. Reaction can be effected at a temperature of from 0 C. to 150 C. A preferred temperature range isfrom 40 C. to C.

The o-disulfophenylimidinyl compounds of the invention are prepared in water or a polar organic solvent which is essentially non-reactive to either the l,2-di(halosulfonyl)benzene or fluorescent amine employed in wthe reaction. Suitable solvents and proportions thereof'aw described hereinbefore. 1 The mono- (X is -CH' and di-"CYQiS X and W are CH -)benzisothiazolylfi dioxide compounds of the invention can be prepared by reaction of a chloromethylaryl-o-sulfonyl chloride with a suitable amine hereinbefore described; The reaction can be carried out at a temperature in the range of 0 C. to C. The proportion of chloromethylaryl-o-sulfon-yl chloride to fluorescent primary amine which can be employed will vary within the range of 0.3:1 "to 3:1 on a molar basis. The proportions of reactants employed to prepare compounds of the formula wherein x is zero or one, will vary as in the case of reactions hereinbefore described. Reaction can be efiec ted by "reacting at a temperature'of from 0 C. to 150 C. A preferred temperature range is from 20 C. to"60 C.

Generally, benzisothiazolyl-S-dioxide compounds of the present invention can be prepared in water, or in a polar organic solvent hereinbefore described. A preferred solvent is water.

The preparation of the optical brighteners of the invention is accompanied by formation of hydrochloric acid by-product. This acid can be neutralized in a conventional manner by addition of a suitable base, e.g., sodium carbonate, sodium bicarbonate, sodium hydroxide, triethylamine, or pyridine to the reaction product. Preferred herein is sodium bicarbonate.

The optical brighteners of the present invention exhibit remarkable stability in the presence of hypochlorite bleach. While applicants do not wish to be bound by any theory as to the nature of such stability, it is believed that the stability is due at least in part to the presence of essential moieties of the formula and to the absence of a free hydrogen attached to a nitrogen atom. These moieties, named herein as substituents on a fluorescent stilbene or coumarin nucleus, e.g., 2- benzisothiazolonyl-S-dioxide o-disulfophenylimidinyl X-S- or 2-benzisothiazolyl-S-dioxide (X=CH provide resistance to the harmful effects of hypochlorite bleaches and resulting loss of fluorescence. Other fluorescent aromatic amines can likewise be rendered resistant to degradative attack by hypochlorite bleaching compounds. Examples of such chromophoric amines are -amino-1,8- naphthalenecarboximides, Z-aminonaphthalenes, 3-amino- 2,5-diaryl pyrroles and the like.

Specific examples of optical brightener compounds of the invention include the following:

(1) 3-phenyl-7- Z-benzisothiazolyl-S-dioxide coumarin (2) 3-phenyl-7-(2-methyl-0-disulfophenylimidinyl) coumarin (3) 3-phenyl-7- (2-methyl-o-disulfophenylimidinyl) coumarin (4) 4-( Z-benzisothiazolonyl-S-dioxide)-4-methylstilbene (5 4-(2-benzisothiazolonyl-S-dioxide)-4-methoxystilbene (6) sodium 4- (2-benzisothiazolyl-S-dioxide)-4'- stilbenesulfonate (7) 4-o-disulfophenylimidinyl-4-phenylstilbene (8) 4-o-disulfophenylimidinyl-3-methoxy-4-methylstilbene (9) 4-(2,2-chlorobenzisothiazolonyl-S-di0xide)-4'- (2,2-methylbenzisothiazolonyl-S-dioxide) -2,2'- stilbenedisulfonic acid 10) disodium 4,4'-di-0-disulfophenylimidinyl-2,2'-

stilbenedisulfonate (1 1) 4,4'-di(Z-benzisothiazolonyl-S-dioxide) -2,2-

stilbenedisulfonamide 12) 4- 2-benzisothiazolyl-S-dioxide -4'- (2-2-chlorobenzisothiazolyl-S-dioxide)-2,2-stilbenedisulfonamide 13) disodium 4,4-di (2-benzisothiazolonyl-S-dioxide)- 6,6'-dichloro-2,2-stilbenedisulfonate (14) disodium 4,4-di 2-benzisothiazolonyl-S-dioxide 3,5-dimethoxy-2,2-stilbenedisulfonate (15) disodium 4,4'-bis 6-methoxy-2-benzisothiazolonyl- S-dioxide) -2,2'-stilbenedisulfonate 16) sodium 4-benzisothiazolyl-S-dioxide-2-stilbenesulfonate The optical brightener compounds of the present invention can be employed for the optical brightening of a wide variety of natural and synthetic materials. Natural materials include organic fibrous materials such as silk and wool. Synthetic fibers include such materials as polyester, polyacrylonitrile, polyamide, acetylized polyvinyl alcohol and polyolefin and cellulose acetate fibers. The brightener compounds of the invention provide excellent brightening and light fastness and can be employed in aqueous or solvent containing brightening compositions. These compositions can contain bleaching components such as hypochlorites without substantial loss of fluorescence.

The optical brighteners of the present invention can be incorporated into polymeric melts and processed to a variety of products including synthetic fibers. Alternatively, they can be applied to a substrate by application of a solution to the surface of a polymeric substrate.

The treatment of fibrous materials can be carried out by immersion of the fibrous materials in an aqueous dispersion of the optical brightening compound of the invention and a surface active agent. Suitable surface active agents include anionic or nonionic compounds such as alkylbenzenesulfonic acid, the condensation product of naphthalenesulfonic acid and formaldehyde or polyoxyethylene alkylether and the like. The fibrous material is immersed in the aqueous dispersion of brightener at a temperature of from 50 C. to C. depending on the kind of fibrous material treated. The fibrous material is normally dried by heating at a temperature of from C. to 220 C. for a time of from 0.5 to 2 minutes.

The brightener compounds of the invention can also be employed in laundry detergent compositions to provide an improved appearance to laundered goods. When so employed they range from 0.01% to 3% of the detergent composition. A preferred amount of brightener is from 0.5% to 1.5%. In addition to these brightener compounds, the laundry detergent compositions of the invention comprise at least 10% of a mixture of an organic detergent and an alkaline builder salt in a ratio in the range of from 5:1 to 1:20, preferably from 2:1 to 1:10. This mixture can be as much as the balance of the composition. The organic detergent compounds and alkaline builder salts are more fully described below.

ORGANIC DETERGENTS tallow, i.e., sodium and potassium tallow and coconut soaps.

(b) Anionic synthetic non-soap detergents.-A preferred class can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic, sulfuric acid reaction products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of these anionic synthetic detergents are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkylbenzenesulfonates, in which the alkyl group can be a straight or branched chain and contains from about 9 to about 15 carbon atoms, preferably about 12-14 carbons; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow' and "coconutoil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts .of sulfuric acid esters of the reaction product ofone .mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) andabout 1 to 6 moles of ethylene oxide; sodium or potassium alkyl phenol ethylene oxide ether sulfates, with 1 to 10 units of ethylene oxide per molecule and wherein the alkyl radicals contain from 8 to 12 carbon atoms; the reaction product of fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; sodium and potassium salts of SO sulfonated C -C a-olefins.

(c) Nonionic synthetic detergents.ne class of nonionic detergents can be broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the hydrophilic or polyoxyalkylene radical which is condensed with any particular hydrophobic group can be readily adjusted to yield a watersoluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. A second class of nonionic detergents comprises higher fatty amides. A third class of nonionic detergents has semi-polar characteristics. These three classes can be defined in further detail as follows:

(1) One class of nonionic synthetic detergents is marketed under the trademark of Pluronic. These detergent compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits Water insolubility, has a molecular weight of from about 1500 to 1800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecule as a whole and the liquid character of the product is retained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation product.

(2) Alkylphenol-polyethylene oxide condensates are condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration with ethylene oxide, the said ethylene oxide being present in amounts equal to to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

(3) Nonionic synthetic detergents can be derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine and include compounds containing from about 40% to about 80% polyoxyethylene by Weight and having a molecular weight of from about 5,000 to about 11,000. Such compounds result from the reaction of ethylene oxide with a hydrophobic base constituted of the reaction product of ethylene diamine and excess propylene OXiClCySfild base having a molecular weight of the order of 2,500 to 3,000.

; (4) Other nonionic detergents include condensation products of aliphatic alcohols having from 8 to 22 carbon atoms, inheither straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 5 to 30 moles of ethylene oxide per .mole of coconut alcohol.

(5) The ammonia', monoethanol and diethanol amides of fatty acids having 'an acyl moiety of from about 8 to about 18 carbon atoms are useful nonionic detergents. These acyl moieties are normally derived from naturally occurring g'lycerides, e.g., coconut oil, palm oil, soybean oil and tallow, but can be derived synthetically, e.g., by

the oxidation of petroleum, or by hydrogenationofcan bon monoxide by the Fischer-Tropschprocess.

(6) Semi-polarnonionic detergents include long chain tertiary amine oxides corresponding to the following general formula l wherein R is an alkyl radical of from about 8 to about 18 carbon atoms, R and R are each-methyhethyl or hydroxyethyl radicals, R is ethylene, and n ranges. from 0 to about 10. The arrow in the formula is a conventional representation of a semi-polar bond; Specific examples of amine oxide detergents include. dimethyldodecylamine oxide and bis-(2-hydroxyethyl) dodecylamineoxide.

(7) Other semi-polar nonionic :detergents include long chain tertiary phosphine oxides corresponding to the following general formula RR'R"P O wherein R is an alkyl, alkenyl or monohydroxyalkyl radical containing from 10 to 20 carbon atoms and R and R." are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a conventional representation of a semi-polar bond. Examples of suitable phosphine oxides are found in US. Pat. 3,304,263 which issued Feb. 14, 1967, and include:v dimethyldodecylphosphine oxide and dimethyl-2-hydroxydodecyl phosphine oxide.

(d) Ampholytic synthetic detergents can be broadly described as derivatives of aliphatic secondary and tertiary amines, in which the aliphatic radical can be straight chain or branched alkyls and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate, or phosphono. Examples of compounds falling within this definition are sodium-3-dodecylaminopropionate and sodium-3- dodecylaminopropane sulfonate.

(e) Zwitterionic synthetic detergents can be broadly described as derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium compounds, in which the aliphatic radical can be straight chain or branched alkyl, and wherein one of the aliphatic substituents contains from about 8 to 24 carbon atoms and one contains an anionic Water solubilizing group, e.g., carboxy, sulfo, sulfato, phosphate or phosphono. Examples of compounds falling Within this definition are 3-(N,N-dimethyl- N-hexadecylammonio)propane-l-sulfonate and 3 (N,N- dirnethyl-N-hexadecylammonio) 2 hydroxy propane-lsulfonate which are preferred for their cool water detergency characteristics. See for example, Snoddy et al., Canadian Pat. 708,148.

These soap and non-soap anionic, nonionic, ampholytic and zwitterionic detergent compounds can be used singly or in combination. The above examples are merely illustrations of the numerous suitable detergents. Other organic detergent compounds can also be used.

BUILDER SALTS The detergent compositions of this invention also contain water-soluble, builder salts either of the organic or inorganic types.

Examples of suitable water-soluble, inorganic alkaline detergency builder salts are alkali metal carbonates, bo rates, phosphates, polyphosphates, bicarbonates, silicates and sulfates. Specific examples. of such salts are sodium and potassium tetraborates, perborates, bicarbonates, carbonates, tripolyphosphate's, pyrophosphates', orthophosphates and hexametaphosphates.

Examples of suitable organic alkaline detergency builder salts are: (1) Water-soluble amino'polyacetates, e.g., sodium and. potassium ethylenediaminetetraacetates, nitrolotriacetates and N- (Z-hydroxyethyD-nitrilo diacetates; (2) Water-soluble salts of phytic acid, e.g-., sodium and potassium phytates-see US. Pat. 2,739,942; (3)

13 Water-soluble polyphosphonates, including specifically, sodium, potassium and lithium salts of ethane-l-hydroxy- 1,1-diphosphonic acid, sodium, potassium and lith um salts of methylene diphosphonic acid, sodium, potassium and lithium salts of ethylene diphosphonic acid, and sodium, potassium and lithium salts of ethane-1,1,2-triphosphonic acid. Other examples include the alkali metal salts of ethane-2-carboxy-1,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethanel-hydroxy-1,1,2-triphosphonic acid, ethane-Z-hydroxy-Ll, Z-triphosphonic acid, propane l,1,3,3 tetraphosphomc acid, propane-1,1,2,2-tetraphosphonic acid, and propane- 1,2,2,3-tetraphosphonic acid; (4) Water-soluble salts of polycarboxylate polymers and copolymers as described in the patent of Francis L. Diehl, US. Pat. 3,308,067 issued March 7, 1967. Specifically, a detergent builder material comprising a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (c) at least 45 mole percent of the monomeric species having at least two carboxyl radicals separated from each other by not more than two carbon atoms; (d) the site of attachment to the polymer chain of any carboxy-containing radical being separated by not more than three carbon atoms along the polymer chain from the site of attachment of the next carboxyl-containing radical. Specific examples are polymers of itaconic acid, aconitic acid, maleic acid, mesaconic acid, fumaric acid, methylene malonic acid, and citraconic acid and copolymers with themselves and other compatible monomers such as ethylene.

Mixtures of organic and/or inorganic builders can be used and are generally desirable. One such mixture of builders is disclosed in Canadian Pat. 755,038 of Burton H. Gedge, e.g., ternary mixtures of sodium tripolyphosphate, trisodium nitrilotriacetate and trisodium ethane-l-hydroxy-1,1-diphosphonate. The above described builders can also be utilized singly in this invention.

The preferred builders are sodium tripolyphosphate and sodium nitrilotriacetate, alone or in admixture. The preferred organic detergents are the anionic sulfate and sulfonates. The detergent compositions preferably provide pHs in the range of about 8.5 to 11.5.

The laundry detergent compositions of this invention can contain, if desired, in addition to the brightener, organic detergent and builder, any of the usual additives for such compositions which make them more attractive or effective. For example, perfumes, dyes, proteolytic enzymes, corrosion inhibitors, oxygen and chlorine bleaches, soil redeposition agents and other brighteners can be used. Diluents such as water, moisture and sodium sulfate can also be used to make up any balance of a composition comprising brightener, organic detergent and alkaline builder salt.

The optical brighteners of the invention are stable to attack by hypochlorite compounds. Accordingly, they are advantageously employed in laundry compositions which contain from 0.5% to 25%, usually 317%, of an activechlorine containing bleaching compound. Examples of such compounds are: dichlorocyanuric acid; 1,3-dichloro 5,5-dimethyl hydantoin; N,N'-dichlorobenzoylene urea; paratoluene sulfondichloroamide; trichloromelamine; N- chloroammeline; N-chlorosuccinimide; N,N'-dichloroazodicarbonamide; N-chloroacetyl urea; N,N'-dichlorobiuret; chlorinated dicyandiamide; sodium hypochlorite; calcium hypochlorite; lithium hypochlorite; chlorinated trisodium phosphate. Preferred compounds are dichlorocyanurates, i.e., dichlorocyanuric acid and the sodium and potassium salts thereof.

In other embodiments of the present invention the optical brighteners are employed in aqueous and granular bleach compositions. In general, aqueous bleach composi- 14 tions are prepared by dissolving or dispersing an optical brightener in an aqueous solution of alkali metal hypochlorite bleach. The optical brighteners of the present invention are readily soluble in aqueous hypochlorite solution and remain stable over an extended period of time so that they can be successfully packaged, shipped and stored without rendering ineffective the whitening action of the optical brightener or the oxidizing action of the bleach. Liquid bleach compositions prepared in accordance with the present invention are characterized by a pH ranging from 10.5 to 13.0 and consist essentially of from 1.0% to 10% alkali metal hypochlorite bleach, from 0.002% to 2% of the optical brightener and the balance water.

Preferred hypochlorite bleach-containing compositions contain the alkali metal hypochlorite bleach component in an amount of from 1% to 10%, preferably from 3% to 7%, with about 5.2% being especially preferred.

The bleach component can be any one of the alkali metal hypochlorites. Examples of such useful bleaches are sodium hypochlorite, potassium hypochlorite, lithium hypochlorite, and the like. However, sodium hypochlorite is highly preferred because of its superior properties and its ready availability.

The optical brightener is present in the liquid bleach compositions of this invention in an amount ranging from 0.002% to 2.0%, preferably from 0.01% to 0.1% with about 0.05% being especially preferred. Dispcrsible polymeric stabilizing or suspending agents can also be employed. Suitable examples are described in US. Pat. No. 3,393,153 to Zimmerer et al., issued July 16, 1968.

The bleach stable brighteners of the present invention are capable of retaining their whitening and brightening eifects even after exposure to aqueous l-10% hypochlorite-containing bleach solutions for extended periods of time, e.g., several weeks of storage. The bleach stability which is normally ascribed to conventional optical brighteners is commonly understood to mean that these optical brighteners are not ineffective when exposed to dilute solutions of bleach for limited periods of time, e.g., at washing machine conditions where the hypochlorite bleach is present in aqueous solutions at about 0.02% hypochlorite level for up to 20 to 30 minutes. In contradistinction to the bleach compatibility commonly understood in the art, the compatibility of the presently claimed optical brighteners is such that they retain their fluorescing effects after exposure to hypochlorite bleach concentrations much higher than normally found in the course of the laundering process.

The desirable bleach compatibility of the optical brighteners of the present invention is employed to advantage in the use of these brighteners in liquid hypochlorite or granular bleach-containing compositions. These compositions normally comprise from 1% to 99% of an active chlorine-containing bleaching compound which is capable of evolving hypochlorite upon contact with water and from 0.005% to 10% of the optical brightener of the present invention. Preferably the granular bleaching compositions of the invention contain from 1% to of the active chlorine-containing bleaching compound, from 2% to 25% of an organic detergent and from 5% to 60% of an alkaline builder salt, said bleaching compounds and builder salts being those hereinbefore described.

The granular-bleach compositions of this invention can contain, if desired, in addition to the bleaching compounds, any of the usual additives for such compositions which make them more attractive or effective, for example, perfumes, dyes, proteolytic enzymes, corrosion inhibitors, other chlorine bleaches, soil redeposition agents and other brighteners may be used.

These granular bleach compositions have a pH ranging from about 8 to 12 and upon dissolution in water evolve active hypochlorite chlorine for the efiective bleaching of cellulosic fabrics.

Preparations of exemplary optical brighteners of this invention ,are described as follows:

EXAMPLE I Preparation of disodium 4,4-(Z-benzisothiazolonyhS- dioxide)-2,2'-stilbenedisulfonate -o 0"o s d, y (I N cs.w

$0.0m SOiONs A solution of 4.78 parts of 2-chlorosulfonylbenzoyl chloride (0.02 mole), 4.14 parts of disodium 4,4'-diamino- 2,2'-stilbenedisulfonate (0.01 mole), 4.86 parts triethylamine and 100 parts dimethylformamide was heated on a steam bath (SO-90 C.) for 3% hours. The reaction was conducted in a ZOO-ml. flask equipped with magnetic stirrer bar, reflux condenser and calcium chloride drying tube. The reaction mixture was distilled under the pressure of a water aspirator and at a bath temperature of 50 C. for two hours to yield a brown-colored residue. The residue was stirred with ml. water and filtered through a sintered glass funnel. The resulting product was dried to yield 7.5 parts of a light tan-colored product which was disodium 4,4-(2-benzisothiazolonyl-S-dioxide -2,2-stilbenedisulfonate.

Infrared spectra (IR), nuclear magnetic resonance (NMR) and ultraviolet (UV) analyses confirmed the structure of the resulting product. NMR spectra indicated a complex aromatic multiplet centered at 1.71 The UV absorption A was 340 nm. and the fluorescence A was 420 nm.

Similar results are obtained when 4-methoxy-4'-amino- 2,2-stilbenedisulfonamide or dipotassium 4,4'-diamino- 6,6 dimethoxy-2,2-stilbenedisulfonate is employed in place of disodium 4,4'-diarnino-2,2'-stilbenedisulfonate in that the following optical brighteners are obtained: 4- methoxy4'-(2-benzisothiazolonyl-S-dioxide) 2,2 stilbenedisulfonamide or dipotassium 4,4'-di(2-benzisothiazolonyl-S-dioxide)-6,6-dimethoxy 2,2 stilbenedisulfonate.

Similar results are obtained when 3-methyl-2-chlorosulfonyl-benzoyl chloride; 4-ethoxy-2-chlorosulfonyl-benzoyl chloride; 3-naphthyl-2-chlorosulfonyl-benzoyl chloride; S-methylsulfonyl-Z-chlorosulfonyl-benzoy1 chloride; 5-ethoxymethyl-Z-chlorosulfonyl-benzoyl chloride; 3- 1,4,7-trioxanonyl)-2-chlorosulfonyl-benzoyl chloride; 3-trifluoromethyl-2-chlorosulfonyl-benzoyl chloride; 4-acetyl-2-chlorosulfonyl-benzoyl chloride; 4-cyano-2-chlorosulfonyl-benzoyl chloride; and 4-( 1,2,3-trihydroxypropyl-2-chlorosulfonyl-benzoyl chloride are employed in place of an equimolar amount of 2- chlorosulfonyl-benzoyl chloride in that the following optical brightener'compounds are formed:

disodium 4,4-(9-methyl-Z-benzisothiazolonyl-S-dioxide)- 2,2'-stilbenedisulfonate; disodium 4,4-(8-ethoxy-2-benzisothiazolonyl- S-dioxide) -2,2-stilbenedisulfonate; disodium 4,4- 9- 1,4,7-trioxanonyl)-2-benzisothiazolyl- S-dioxide]-2,2'-stilbenedisulfonate; it disodium 4,4'-(9-trifiuoromethyl-Z-benzisothiazolonyl-- I S-dioxide)-2,2'-stilbenedisulfonate; disodium 4,4'-.(8-acetyl-Z-benzisothiazolonyl-S-dioxide)- 2,2'-stilbenedisulfonate; a disodium 4,4-(8-cyano-2-benzisothiazolony -S-dioxide)- 2,2'-sti1benedisulfonate; and I r disodium 4,4'-[8-(1,2,3-trihydroxypropyl)-2-benzisothiazolonyl-S-dioxide] 2,2'-stilbenedisulfonate.

16 I EXAMPLE II- Preparation of disodium 4,4-(b disulfophenylimidinyn- 3 2,2'-stilbenedisulfonate i SOzONa. SOzONa S- The apparatus of Example I was employed. Two parts (7.57 10- moles) of 1,-2-di(chlorosulfonyl)benzene, 1.57 parts (3.78X10 moles) of disodium 4,4'-diamino- 2,2'-stilbenedisulfonate, 1.27 parts of sodium bicarbonate and 10 parts distilled water were added to the reaction vessel. The reaction mixture was heated on a steam bath for 14 hours (90 C.). The resulting solution, yellowcolored, was cooled to 0 C. and filtered through a sintered glass funnel to yield- 0.3 part disodium 4,4'-(0- disulfophenylimidyl)stilbenedisulfonate, the desired product. An additional 2.5 parts of the desired product were isolated from the aqueous filtrate by concentrating the filtrate to dryness, extracting with ml. of boiling methanol, filtering, recrystallizing by addition of 100 ml. diethylether and filtering the solid product.

Cale: C, 33.7; H, 3.03; N, 3.02. Found: C, 33.0; H, 2.7; N, 3.0.

IR, NMR and UV analyses confirmed the structure of the resulting product, NMR spectra indicated a complex multiplet centered at 1.97". The UV absorption A was 314 nm. and the fluorescence A was 425 nm.

Similar results are obtained when 2-methyl-4,4-diamino-2'-stilbenesulfonamide; 2-ethoxy-4,4'-diamino-2'-stilbenesulfonamide; 2,4-dichloro-4'-amino-2'-stilbenesulfonamide;' and disodium 4,4-diamino-6-methoXy-2,2-stilbenedisulfonate are employed in place of 4,4-diamino-2,2'-stilbenedisulfonate in that the following optical brighteners are obtained:

4,4'- o-disulfophenylimidinyl) -2-methylstilbenesultona mide;

4, 4- o-disulfophenylimidinyl) -2-ethoxystilb enesulfonamide;

2,4-dichloro-4-(2-benzisothiazolony1-S-dioxide)- '-stilbenesulfonamide; and

disodium 4,4'-di (Z-benzisothiazolonyl-S-dioxide) 6-methoxy-2, 2'-stilbenedisulfonate.

EXAMPLE III I Preparation of disodium 4,4-(2-benzisothiazolyl- S-dioxide)-2,2'-stilbenedisulfonate v r C SOz ONa--. SOZONB 01a.

The apparatus of Example ,I was employed. 4,02 parts of a mixture 'of u-bromo-o-toluenesulfonyl chloride and qc hloro-o-toluenesulfonyl chloride (preparedby refluxing a solution of 95 .5 parts o-toluenesulfonyl chloride, parts --1T-b romosuccinimide, 3 par ts benzoyl peroxide and .600 ml. carbon tetrachloride for .8 hours; cooling the reaction mixture; removing solids, by filtration; washing with, carbon tetrachloride; distilling at water .aspirator pressure and a bath temperature of 50 C.; and distilling the residue to provide a colorlessoil of B.'P. 124-130 C. at 0.6 mm.pressure), 3.48 parts disodium 4,4-diamino-2,2'- stilb'en'edisulfonate, 378' parts sodium bicarbonate and 25 parts water were heated'on a steam bath 80-90 C. for 48 17 hours. The reaction mixture was cooled to C. and filtered through a sintered glass funnel to provide 2.2 parts of the desired product, 4,4 (2 benzisothiazolyl-S-dioxide)-2,2-stilbenedisulfonate. An additional 2.0 parts of product were recovered from the aqueous filtrate by extraction with methanol and re-crystallization with diethylether.

Calc.: C, 42.6; H, 3.42; N, 3.42; S, 16.25. Found: C, 42.58; H, 3.44; N, 3.03; S, 16.9.

IR, NMR and UV analyses confirmed the structure of the resulting product. NMR spectra indicated a singlet at 4.55-r and a complex multiplet centered at 1.751. The UV absorption A was 332 nm. and the fluorescene A was 409 nm.

Similar results are obtained when sodium 4,4'-diamino-2-methylsulfonyl-2-stilbenesulfonate;

sodium 4,4'-diamino-5-eth0xymethyl-2'-stilbenesulfonate;

sodium 4,4'-diamino-S-trifluoromethyl-Z'-stilbenesulfonate;

sodium 4,4'-diamino-2-propionyl-2'-stilbenesulfonate are employed in place of 4,4'-diamino-2,2-stilbenedisulfonate in that the following optical brighteners are obtained:

4,4'- (2-benzisothiazolyl-S-dioxide) 2-methy1sulfonyl- 2'-stilbenesulfonate;

4,4- (2-b enzisothiazolyl-S-dioxide) 5-ethoxymethy1- 2'-stilbenesulfon ate;

4,4'- (2-benzisothiazolyl-S-dioxide) 5-trifluoromethyl- 2-stilbenesulfonate;

4,4'- (2-b enzisothiazolyl-Sedioxide) 2-propi0nyl- 2'-stilbenesulfonate; and

4,4'- (2-b enzisothiazolyl-S-dioxide) 2-cyano- 2'-stilbenesulfonate.

EXAMPLE IV (a) Preparation of 4,4'-bis(2-benzisothiazolyl-S-dioxide)- 2,2'-stilbenedisulfonyl chloride 0 o 0 o f N H=CH -N\ l ch/ solo! S0201 cm A suspension of 8.72 parts of disodium 4,4'-(2-benzisothiazolyl-S-dioxide) 2,2 stilbenedisulfonate, 20 parts thionyl chloride and 300 parts of dimethylformamide was stirred at ambient temperature of 15 minutes. The resulting solid product was filtered, washed with water, acetone and dried to give 8.63 parts of 4,4-(2-benzisothiazolyl-S- dioxide)-2,2'-stilbenedisulfonyl chloride. NMR, IR and elemental analyses confirmed formation of the desired compound.

Calc.: C, 47.3; H, 2.83; N, 3.94; Cl, 9.97. Found: C, 47.2; H, 3.2; N, 4.1; Cl, 10.5.

(b) Preparation of 4,4-(2-benzisothiazolyl-S-dioxide)- 2,2-stilbenedisulfonamide A suspension of 7.1 (0.01 mole) parts of 4,4'-(2-benzisothiazolyl-S-dioxide) 2,2 stilbenedisulfonyl chloride prepared as described in part (a) above, 5 parts of 28% ammonium hydroxide, parts pyridine and 100 parts of dimethyl formamide was stirred at ambient temperature for three hours. The solid was filtered, washed with water, acetone and dried to give 5.9 parts of 4,4'(2-benz.iso-

18 thiazolyl-S-dioxide)-2,2'-stilbenedisulfonamide. NMR, IR, UV and elemental analyses confirmed the formation of the desired compound. The UV A was 332 nm. and the fluorescence h was 425 nm.

(0) Preparation of 4,4-(2-benzisothiazolyl-S-dioxide)- 2,2-stilbenedisulfonyl amide 4,4-(2-benzisothiazolyl-S-dioxide) 2,2 stilbenedisulfonyl chloride prepared in part (a) above was reacted with morpholine, diethanolamine, glucosamine, aniline, diethylamine and Z-ethylaminoethanol in the manner described in part (b) above. In each instance an equimolar amount of amine was employed in place of the ammonium hydroxide of part (b). The resulting optical brightener compounds conforming to the formula N GH- R CH3 O2N\ and the definitions of R and R are described, respectively, in Table 1 as follows:

EXAMPLE V (a) Preparation of disodium 4-arnino-4'-(1-phthalimidinyl)2,2'-stilbenedisulfonate N/ soloNa soiona c i A solution of 1.33 parts (0.01 mole) of phthalide, 4.68 parts (0.01 mole) of disodium 4,4'-diaminostilbene- 2,2'-disulfonate, 0.02 parts of N,N-dimethyldodecylamine and 30 parts of ethylene glycol was. heated on the steam bath (95 C.) for 18 hours. The reaction was conducted in a -ml. one-necked flask fitted with a reflux condenser and calcium chloride drying tube. The reaction mixture was cooled to 20- C., 300 parts of ethanol were added and the solution was filtered. Addition of 300 parts of diethylether to the filtrate followed by filtration yielded 3.0 parts of a light-tan solid which was disodium 4-amino- 4'-(I-phthalimidinyl)2,2'-stilbenedisulfonate. IR, NMR and UV analyses confirmed the structure of the resulting product.

Calc.: C, 40.3; H, 4.57; N, 4.27. Found: C, 40.26; H, 4.65; N, 4.53.

A solution of 1.9 parts of a-bromo-o-toluenesulfonyl chloride with a-chloro-o-toluenesulfonyl chloride (as prepared in Example III), 3.77 parts of disodium 4-amino- 4'-(1-phthalimidinyl) 2,2 stilbenedisulfonate and 1.8 parts of sodium bicarbonate in 20 parts of water was heated on a steam bath (8090 C.) for 16 hours. The resulting solution was cooled to C. and filtered to give 0.9 parts of the desired compound, disodium 4-(2-benzisothiazolyl-S-dioxide)-4'-(l-phthalimidinyl) 2,2 stilbenedisulfonate. An additional 4.0 parts of the product were isolated from the aqueous filtrate. NMR, IR, UV and elemental analyses confirmed formation of the desired optical brightener.

Ca1c.: C, 38.83; H, 4.89; N, 3.12. Found: C, 38.35; H, 3.88; N, 3.14.

NMR spectra indicated a doublet at 4.751- and a multiplet centered at 1.851: The UV absorption A was 325 nm. and the fluorescence A was 440 nm.

(0) Preparation of 4-(2-benzisothiazolyl-S-dioxide)-4'-(1- phthalimidinyl)-2,2'-distilbenesulfonyl chloride ((1) Preparation of 4-(Z-benzisothiazolyl-S-dioxide)-4'-(1- phthalimidinyl)-2,2'-stilbenedisulfonamide A suspension of 6.8 parts (0.01 mole) of 4-(2-benzisothiazoIyl-S -dioxide) -4'- l-pht halimidinyl stilbene-'2,2 '-disiulfonYl ch1oride,"5parts' 'of28% ammonium hydroxide, 1 part pyridine and parts of dimethylformamide was stirred at ambient temperature'for three hours. The solid was filtered, washed with water, then acetone, and dried to give' ijparts of 4-(IhbenlnisdthiaeolyLS-dioxide)-4'-('1 phthalimidinyl)stilbene 2,2' disulfonamide.

" IR,"NMR and. UV analyses confirmed-"the structure-6f thefre sulting product. NMR spectra indicated asingie't a't 4.89?- and 3.501 andfa n mum-inc" multiplet' cente fedat abo't 2.0+."The UV absorption a was 325 um? and .thafluq iss iwsit eyi 'repsaasn of 4 (Z bnZisothiaZoIyi-S-dioxide U '4 phthalimidinyl)-2,2;distilbenesulfonamides' f 20 idinyl)-2,2'-distilbenesulfonyl chloride, from part (c) .flb ve; w wa ed hma iue. ao i 'an "anilineinplace of the ammoniurnhydroxide in part (d) above' The compounds corresponding to the formula and the definitions of R and R are described, respectively, in Table 2 as follows: 1

EXAMPLE VI Preparation of sodium 4-(2-benzisothiazolonyl- S-dioxide)-2-stilbenesulfonate SOgONa The solution obtained by dissolving 2.39 parts (0.01 mole) of 2-chlorosulfonyl-benzoyl chloride, 3.1 parts (0.01 mole) of sodium 4-aminmZ-stilbensulfonate, and 1.1 parts of triethylamine and 100 parts of dimethyl formamide are heated in a SOD-ml. one-necked flask equipped with a magnetic stirrer bar and reflux condenser. Thereaction vessel is heated at a temperature of -90 C. for 16 hours. The reaction product is distilled under the pressure of a water aspirator and at a bath temperature of 50 C. to provide a solid residue which is washed with water, filtered and dried to provide the desired product, sodium 4 (2-benzisothiazolonyl-Sdioxide)-2-stilbenesulfonate. The compound is a'bleach-stable optical brightener.

Similar results are obtained. when 4-bromo-2-chlorosulfonylbenzoyl chloride; 4-methoxy-Z-chlorosulfonyl benzoyl chloride; and 4-methyl-2-chlorosulfonyl-benzoyl chloride are'employed in'plac'e of o-chlorosulfonyl-benzoyl chloride in that the correspondingly substituted optical brightener compounds are obtained, respectively, as follows:

sodium 4=( ii-bron'io-2ebengisothiazolonyl-S-dioxide) that thefollowing optical brightgnercompoutidSareobsodium 4-(2-benzisothiazolonyl-S-dioxide)- 2-stilbenesulfonate;

4-(2-benzisothiazolonyl-S-dioxide)-4-ethoxy- 2,2'-stilbenedisulfonic acid;

disodium 4-(2-benzisothiazolonyl-S-dioxide)- 4-methoxy-2,2'-stilbenedisulfonamide, and

4-(2-benzisothiazolonyl-S-dioxide) -2-stilbenesulfonic acid.

EXAMPLE VII Preparation of 3-phenyl-7-(o-disulfophenylimidinyl) coumarin The solution obtained by adding 2.37 parts (0.01 mole) of 7-amino-3-phenylcoumarin to 2.75 parts (0.01 mole) of 1,2-di(chlorosulfonyl)benzene and 10 parts of water is heated on a steam bath (80-90 C.) for a period of 14 hours. The heating is conducted in a 50-ml. one-necked round-bottomed flask equipped with a reflux condenser. The resulting solution is cooled to C. and filtered through a sintered glass funnel to provide the desired product, 3-phenyl-7-(o disulfophenylimidinyl)coumarin. An additional portion of the desired product is isolated from the aqueous filtrate by concentrating the filtrate to dryness, extracting with methanol, recrystallizing with diethylether and filtering the product. The resulting com-- pound is an optical brightener having bleach-compatibility properties.

Similar results are obtained when 7-amino-4-phenylcoumarin; 7-amino-5-chlorocoumarin; 7-amino-3-phenyl- 8 methoxycoumarin; 7 amino 3 methylcoumarin; 7- amino-3,5,8-trimethoxycoumarin; 7 amino-3,5-diphenylcoumarin; 7-amino-3-phenyl-S-chloromethylcoumarin; 7- amino--(3',5,7'-trioxanonyl)-3-phenylcoumarin are employed in place of 7-amino-3-phenylcoumarin in that the following bleach-stable optical brightener compounds are formed:

7- (o-disulfophenylimidyl) -4-phenyl coumarin;

7- o-disulfophenylimidyl) -5-chlorocoumarin;

7- (o-disulfophenylimidyl) -3-phenyl-8-methoxycoumarin;

7- a-disulfophenylimidyl) -3-methylcoumarin;

7- (o-disulfophenylimidyl) -3 ,5, S-trimethoxycoumarin 7- (o-disulfophenylimidyl) -3,5-diphenylcoumarin;

7- (o-disulfophenylimidyl) -3 -phenyl-5-chloromethylcoumarin;

7-(o-disulfophenylimidyl -5 3',5',7'-trioxanonyl) 3-phenylcoumarin.

Similar results are obtained when the 1,2-di(chlorosulfonyl)benzene of Example VII is replaced with an equimolar amount of 2chlorosulfonyl-benzoyl chloride or u-chloro-o-toluenesulfonyl chloride in that the resulting optical brightener compounds are 3-phenyl-7-(2-benzis0- thiazolonyl-S-dioxide)coumarin and 3-phenyl-7-(2-benzisothiazolyl-S-dioxide coumarin.

EXAMPLE VIII (a) Preparation of disodium 4-amino-4-phthalimidyl-2,2'-stilbenedisulfonate 0 II o \N CH=CH NHz o smom SO ONa (b) Preparation of disodium 4-(2-benzisothiazolonyl- S-dioxide)-4'-phthalimidyl-2,2'-stilbenedisulfonate i @Q Q SO ONB The solution obtained by admixing 5.44 parts (0.01 mole) of the product of part (a) above, 2.39 parts (0.01 mole) of 2-chlorosulfonyl-benzoyl chloride, 1.01 parts of triethylamine and 100 parts of DMF is heated on a steam bath (90 C.) for 16 hours. The solution is heated in a 250-ml. one-necked round-bottomed flask equipped with a reflux condenser and a calcium chloride drying tu-be. Upon completion of the heating period, the solvent is distilled at water aspirator pressure and a bath temperature of 50 C. to provide a solid residue. The residue is washed with water and filtered through a sintered glass funnel and dried to provide the desired product, disodium 4-(2-benzisothiazolyonyl S dioxide)-4-phthalimidyl-2,2'-stilbenedisulfonate.

EXAMPLE IX (a) Preparation of disodium 4-amino-4'-(2-benzisothiazolonyl-S-dioxide)-2,2'-stilbenedisulfonate C SOzONB SOgONfl reflux condenser and a calcium chloride drying tube. The

reaction mixture is distilled at water aspirator pressure and at a bath temperature of 50 C. for three hours to 23 yield a solid residue. The residue is stirred with water and filtered through a sintered glass funnel. The resulting product is washed with acetone and dried to yield disodium 4-amino-4'-(2-benzisothiazolonyl S dioxide)2, 2'-stilbenedisulfonate.

(b) Preparation of disodium 4-(l-isoindolinyl)-4-(2- benzisothiazolonyl-S-dioxide) -2,2'-stilbenedisulfon ate A suspension of 5.79 parts (0.01 mole) of disodium 4-amino-4-(2-benzisothiazolyonyl S dioxide)-2,2'-stilbenedisulfonate, prepared as described in Example IX(a), 2.64 parts( 0.01 mole) of o-xylene dibromide, 0.84 part of sodium bicarbonate and 50 parts of water is heated on a steam bath -(8090 C.) for a period of 14 hours. The reaction is conducted in a 100-ml. flask fitted with a reflux condenser. The resulting solution is cooled to C. and filtered through a sintered glass funnel to provide the desired product.

A bleach-stability test was performed to evaluate the bleach compability of the brighteners of the present invention in concentrated aqueous hypochlorite-containing solution.

A bleach-stability test was performed to evaluate the bleach compatibility of the brighteners of the present invention in concentrated aqueous hypochlorite-containing solution. Aqueous sodium hypochlorite solutions containing approximately 5.25% sodium hypochlorite and 0.5% of the compounds of Examples I to IV were formulated by dissolving the optical brightener in the aqueous hypochlorite-containing solutions. The resulting solutions were visually examined periodically under ultraviolet light for fluorescence. The solutions continued to exhibit strong fluorescence after a storage period of four hours indicating a high degree of stability under extremely adverse hypochlorite degradative conditions.

The detergent (laundering and brightening) compositions of this invention are exemplified by the following examples which describe built formulations in which the optical brighteners of the invention can be employed. These compositions provide pHs in the range of 85-115. The invention is not limited by these examples, however, which are merely illustrative.

The composition launders well and exhibits good brightening properties on cotton fabrics.

.EXAMP DE XI A granular built synthetic detergent composition having the following formulation can be prepared with the brightening agents of this invention incorporated therein. The composition, in addition to performing well in its 2.4 cleaning capacity, imparts eifective fluorescence to fabrics cleanedinthe solution. I k

' Percent fective chlorine bleaching agent performs very well in cleaning, whitening and brightening;

. Percent Sodium tallow alkyl sulfate 7 Sodium linear dodecylbenzenesulfonate 7 Sodium tripolyphosphate 50 Sodium carbonate g g 10 Sodium sulfate 10 Potassium dichlorocyanurate 15 4,4'(Z-benzisothiazolyl-S-dioxide) 2,2 stilbenesulfonate 0.05 Moisture Balance EXAMPLE XIII A built liquid laundering composition which brightens as it cleans and which is suitable for laundering household fabrics can have the following composition:

Percent Sodium-3-dodecylaminopropionate 6 Sodium linear dodecylbenzenesulfonate 6 Potassium pyrophosphate 20 Potassium toluene sulfonate l i." 8 Sodium silicate 3.8 Carboxymethyl hydroxyethyl cellulose 0.3 4-(2 benzisothiazolyl-S-dioxide) 4 4 (1 phthal imidinyl)-2,2-stilbenedisulfonate L i 0.05 Water Balance This detergent composition is eifective in laundering and brightening resin-treated cotton wash and wear fabrics.

EXAMPLEXIV A household laundering composition has the following ingredients: i

Percent Sodium salt of SO -sulfonate tetradecene 10 Dimethyl coconut alkyl ammonio acetate 10 Trisodium ethane-hydroxy triphosphonate 60 Sodium carbonate 10 4,4'-(Z-benzisothiazolyl-S-dioxide) 2,2 stilbene if. Y

disulfonamide 0.10 Moisture Balance This composition brightens as it cleans and can be usefully employed in laundering nylon fabrics.

EXAMPLE Xv An effective granular detergent composition'has the following formulation; I

Percent Sodium linear dodecylbenzenesulfonate i 1.1. 7.5 Sodium tallow alkyl sulfate ...1 2 Hydrogenated marine oil fatty acid suds depressant 2.2 Sodium tripolyphosphate 40 Trisodium nitrilotriacetate a' 20 Sodium silicate (ratioSiO :Na O of 2,: 1) S 10 Water Balance,

25 EXAMPLE XVI Another efiective granular detergent has the following composition:

Percent Sodium linear dodecylbenzenesulfonate l Condensation product of 1 mole of nonyl phenol with EXAMPLE XVII A laundering-brightening composition, especially effective on cotton fabrics at cool water temperatures, has the following composition:

Percent Sodium tallow alkyl sulfate 3-(N,N-dimethyl-N-dodecylammonio) 2 hydroxypropane-l-sulfonate 12 Sodium salt of So -sulfonate a tridecene 5 Sodium tripolyphosphate 30 Trisodium nitrilotriacetate 20 Sodium silicate (SiO Na O=1.6:1) Sodium sulfate 10 Sodium carboxymethyl hydroxyethyl cellulose 0.3

3 phenyl-7- (2-benzisothiazolonyl-S-dioxide couma rm 0.1 3-phenyl-7-(2-benzisothiazolyl S dioxide)-coumarin 0.1 Moisture Balance The aqueous and granular bleach composition of this invention are exemplified by the following examples which are formulations in which the optical brighteners of the invention can be employed. The invention is not, however, limited by these examples which are merely illustrative.

EXAMPLE XVIII An excellent aqueous bleach composition which improves the whitening of bleached textiles has the following composition:

An aqueous bleach having advantageous bleaching and whitening has the composition:

'Percent Sodium hypochlorite 5.2 Disodium 4-(Z-benzisothiazolyl-S-dioxide) 4' (2- phthalimidinyl)-2,2'-sti1benedisulfonate 0.05

Water Balance 26 'EXAM'PLE XX The following granular bleach composition which dissolves readily in a household automatic washing machine has the following composition:

Percent Potassium dichlorocyanurate Sodium linear dodecylbenzenesulfonate 6 Potassium pyrophosphate 25 Disodium 4-(1-isoindolinyl) 4' (2-benzisothiazolonyl-S-dioxide)-2,2-stilbenedisulfonate 3 Moisture 0.3 Sodium sulfate Balance Similar results are obtained when sodium dichlorocyanurate is employed in place of potassium dichlorocyanurate in that a bleaching and brightening composition is obtained.

The foregoing description of the invention has been presented describing certain operable and preferred embodiments. It is not intended that the invention should be limited since variations and modifications thereof will be obvious to those skilled in the art, all of which are within the spirit and scope of this invention.

What is claim is:

1. A compound of the formula D An Aa N wherein each a is an integer of from 1 to 4; each A is selected from hydrogen; alkyl of 1 to 10 carbon atoms; halogen; alkoxy of from 1 to 10 carbon atoms; aryl of from 6 to 12 carbon atoms; alkylsulfonyl of from 1 to 10 carbon atoms; alkoxyalkyl of from 2 to 10 carbon atoms; polyethylenoxy of the formula H(CH 'CH O) where n is an integer from 1 to 10; haloalkyl of from 1 to 10 carbon atoms; alkanoyl of from 2 to 10 carbon atoms; cyano; polyhydroxyalkyl of from 1 to 10 carbon atoms; X is selected from and each p is 1 or 2.

2. A compound according to Claim 1 which is 3-phenyl-7-(o-disulfophenylimidinyl) coumarin.

References Cited UNITED STATES PATENTS 3,711,474 1/ 1973 Lyness et a1. 260-240 CA HENRY R. IILES, Primary Examiner C. M. S. JAISLE, Assistant Examiner 

